Reactive disazo dyestuffs



United States Patent M 3,377,335 REACTIVE DISAZO DYESTUFFS- RudolfDiirig, Basel, andiWerner B0ssard, Riehen,n

Switzerland, assignors to J. R. .Geigy; A.G., Basel, Switzerland NoDrawing. Filed Sept. 14, 1964, Ser. No. 396,422

Claims priority, applicationSwitzerland, Sept. 18, 1963, 11,524/63 7Claims. (Cl. 260-146) ABSTRACT OF THE DISCLOSURE,

Fiber-reactive disazo-dyestuifs are provided. Suchdyestuffs in the freeacid form represent a member selected from the group consisting of abenzene-azo-benzene-azonaphthalene disazo-dyestutf' and abenzene-azo-naphthalene-azo-naphthalene disazo-dyestuff, themetallizable substituents of which member are in ortho-positions tothe-azo bridge linking the terminal naphthalene nucleus to the remainderof the dyestuif molecule, and the fiberreactive grouping of which memberis-a 2,4,5-trichloropyrimidyl-(6)-amino-group linked to the terminalbenzene nucleus, said member containing a total-of from 2- to 4 --SO Hgroups at least two of which are at the terminal naphthalene nucleus.The invention also provides, 1:1 copper metal complexes .of the disazodyestuffs.

The present invention concerns new reactive, coppercontaining disazodyestuffs, a process for the production thereof, their use for thedyeing;of cellulose and polyamide material as well as, as industrialproducts, the material dyed therewith.

Thetnovel reactive dyestuffs accordingto the invention are: (a)fiber-reactive sulfonated metallizable .disazo dyestuifs of thebenzene-azo-benzeneazo-naphthalene series and of thebenzene-azot-naphtlralene-azo-naphthalene series, the metallizablesubstituents of which are in orthoposition to the azo bridge linking theterminal naphthalene nucleus to the remainder-of the dyestufi molecule,and the fiber reactive groupingofiwhich is the2,4,5-trichloropyrimidyl-(6)-amino group andis linked, in-contrast toknown disazo dyestutfs ofthe' above-mentioned series, to the terminalbenzene nucleus, and :(b) ;the copper 1:1 complexes;of.,the-aforesaidmetallizable disazo dyestuffs.

These dyestuffs acordingtto the invention are sulfonated by at least twoSO H groups at the terminal naphthalene nucleus, and from 010 2further-SOgHgroups in the, dyestufi molecule;

Especially valuable as dyestuffs .for the "fiber-materials describedhereinafter,- due to theirgood all-around dyeing properties, are thedyestuffs according to the inventionwhich in their free acid form fallunder the formula- 3,377,335 Patented Apr. 9, 1968 wherein:

oneof X andX ,representszhydrogensand theothenthe2,4,5-trichloropyrirnidyle(6)=amino group,

Y represents hydrogen,. lower: alkyl,. lower; alkoxy or S0 H, lzrepresents hydrogen-,1 lower. alkyl, lowerv alkoxy hydroXy-lower;alkoxy or lowerralkoxy-lower-alkoxy, and

Z repersents' hydrogen, or

Z and'Z when'itaken;togetherrepresent the grouping Rt representshydrogen,- lower alkyl, hydroxy-lower alke oxyor lower alkoXy-loweralkoxy, and,

represents a hydroxynaphthyl iradical the hydroxylv group of which is inortho-position to the azo-bridge, or under the formula X o cu l X2 Zi Z2(IB) wherein X X Y, Z Z and? have the same meanings as thecorresponding:substituents:

amount of dyestuif fixed on the fiber amount of dyestuif drawn on thefiber The latter amountof dyestuif drawn on the fib'eris the amount ofdystuff which hasb'een deposited on-the fiber,

during dyeing and is present thereon after-thedyed fiber material hasbeen removed from the dyebath.

The former amount of dyestuif is that which remains on the fibermaterial after the conventional soaping of material after the same hasbeen removed from .the dyebath.-

lnfollowing conventional practice both amounts are given hereinafter inpercent of the amount of dyestulf initially present in the dyebath.

The above ratio is a measure of the practical usefulness of a reactivedye in commercial dyeing processes, a ratio of 1:2 being the permissibleminimum.

Moreover, many of the above-mentioned known dyestuifs having thereactive grouping at the naphthalene nucleus are excessively substantiveand therefore lead to dyeings, especially on cotton or staple fiberwhich lack wash fastness.

The new metallizable, and especially the new coppercontaining reactiveazo dyestuffs according; to the invention dye cellulose materials suchas staple fiber, jute, ramie, hemp and, in particular, cotton, but alsopolyamide fibers such as natural fibers like wool or silk, or syntheticfibers such as nylon, in blue, navy blue, green, grey or grey-blackshades which have excellent wet fastness and also good light fastnessproperties.

Cellulose fiber materials are advantageously dyed with the dyestuffsaccording to the invention by the exhaustion method under theconventional conditions for dyeing with fiber-reactive dyes, i.e. byintroducing the cellulose fibers to be dyed into a dye bath of longliquor ratio which contains an acid binding agent and, optionally, alsoneutral salts such as sodium chloride or sodium sulfate, at a slightlyraised temperature, gradually heating the bath to temperatures of 80 to100 C. and completing the dyeing process by fixing of the dyestutf onthe fiber at this temperature. If desired, the above-mentioned neutralsalts which accelerate the drawing of the dyestulfs on the fibers can beadded to the bath only after the actual dyeing temperature has beenattained.

Moreover, cellulose fiber material can also be padded or printed, forexample, at a low temperature, with a thickened dyestuff solution andthe dyestutf is then fixed by treatment with acid binding agents.Examples of such agents are sodium or potassium carbonate, diandtrisodium phosphate, sodium hydroxide solution and, at temperatures ofover 50 C., also sodium or potassium bicarbonate.

The treatment with these agents can be performed at room temperature orat a raised temperature. Instead of an alkaline after-treatment of thealready impregnated material, the acid binding agent can be added inmany cases to the impregnating liquors or printing pastes, and then thedyeing is developed by a short heating at temperatures of over 100-160C., or by storing for a longer time at room temperature.

The new dyestuflis are chemically bound to the fiber molecules by thetreatment with acid binding agents and, after soaping to removenon-fixed dyestutf, the cellulose dyeings in particular have excellentwet fastness properties, as mentioned here'mbefore.

The fiber reactive disazo dyestufis according to the invention areobtained by reacting an amino disazo dyestuff containing at least twowater solubilizing groups of the formula wherein:

one of X and X represents hydrogen. and the other the primary aminogroup, and Y, Z Z R and have the above given meanings in any orderdesired with an agent giving off copper, and with2,4,5,6-tetrachloropyrimidine, to form the corresponding dyestufi ofFormula IE, or without the copper-yielding agent, to form a dyestufi" ofFormula IA.

as the radical of a coupling component of the hydroxynaphthalene seriescoupled in ortho position to the hydroxyl group, is a di-sulfonated1-hydroxynaphthyl-(2) or 2-hydroxynaphthyll) radical.

Advantageously (I)H A represents a dior tri-sulfonatedl-hydroxynaphthyl-(Z) radical.

The amino disazo dyestuff used as starting material of Formula II isobtained, for example, by coupling the diazonium compound of an amine ofthe formula X NH2 X9" (III) wherein one of X and X represents hydrogenand the other a substituent which can be converted into the primaryamino group such as the nitro group or an acylamino group, in the lattercase it is preferably a carbacylamino group such as the acetylamino orbenzoylamino group, and Y has the meaning given in Formula II, with acoupling component of the formula wherein R, Z and Z have the meaningsgiven in Formula IA. The amino monoazo dyestuif is then diazotized,coupled with a coupling component of the formula wherein A has themeaning given in Formula IA, and X and X in the disazo dyestuff obtainedis converted into the amino group X or X by either reducing the nitrogroup or saponifying the acylamino group.

Advantageously, the amino disazo dyestuif of Formula II is firstcoppered and then the copper complex obtained is reacted with2,4,5,6-tetrachloropyramidine to form the end product of Formula IB. Theamino disazo dyestufi is coppered preferably with water solublecopper-(II) salts, in particular with copper-(II) sulfate, in a weaklyacid to alkaline medium, in the latter case particularly an ammoniaalkaline medium, optionally in the presence of water-soluble organicbases such as dialkylamines, pyridine or dimethyl formamide.

The copper-containing amino disazo dyestufr is reacted with 2,4,5,6tetrachloropyrimidine advantageously in aqueous or aqueous-organicmedium at a raised tempera ture and, preferably, in the presence ofagents which butter acid. The organic part of the aqueous-organic reaction medium consists, in particular, of organic solvents which aremiscible with water, such as lower alkanols, e.g. methanol or ethanol;lower aliphatic ketones such as acetone; amides of lower fatty acidssuch as formamide or dimethyl formamide, or dioxan. Chiefly, alkalimetal salts of lower fatty acids, e.g. sodium acetate, are used asagents which bufier acids.

The following non-limitative examples serve to illustrate the inventionfurther. Where not otherwise expressly stated, parts are given as partsby weight. The temperatures are in degrees centigrade. The relationshipof parts by volume to parts by weight is as that of milliliters (ml) tograms (g.).

5 light. Synthetic resin finishing causes neither change in shade norworsening of the fastness to light.

Similar dyestuifs having equally good fastness properties are obtainedif, instead of the amino disazo dyestuff described in the example, theequivalent amount of an amino disazo dyestuif formed from the componentsgiven in Table I is coppered under the conditions described in theexample and reacted with 2,4,5,6-tetrachloropyrimidine.

TABLE I No. Nitrodiazonium compound from Hydroxy compound Aminobenzenecompound Shade on cotton 2 z-amino-s-nitro-l-methoxybenzene1-h%droxyna)hthalene-3,6,8-trisull-amino-El-methoxybenzene Greenish navyblue.

p onic aci 3 2 amin0-5nitr )4-rnethyl-l-meth0xycdo1-an1ino-3-methy1benzene Do,

benzene.

4 2-amino 5-nitr0-1,4-diethoxybenzene d "do 52-amino-5-nitro-1-metl1oxybenzene d0 l-animobenzene 6 .do2-hydr0xynaphthalene-I,,6,8-trisu1- 1-amino-3-methylbenzene phonic acid.7 "do ..d

2-amino-5-nitrol ,4-di-(fl-hydroxyethoxyybenzene. phonic acid 92-amino-5-nitro-1-etl1oxybenzene do 10 2-amino5-nitro-l-hydroxybenzenedo0 l-animobenzene 1-hydroxynaphthalene-B,6,8-trisuldo D0. Olive green.

Navy blue. Do.

EXAMPLE 1 65.1 parts of the amino disazo dyestuff of the formula 0011 (m$10311 NH N=N N= 3H; H038 i SOaH produced by coupling diazotised2-amino-5-nitrol-methoxybenzene with l-hydroxynaphthalene3,6,8-trisulphonic acid in acetice acid solution, reducing the nitrogroup with sodium sulphide, diazotising the amino monoazo dyestuffobtained and coupling the latter with 1-amino-3- methylbenzene in thepresence of excess sodium acetate, are dissolved in 1000 parts of waterand parts of ammonia. 50 parts of diethylamine and parts of coppersulphate in 100 parts of water are added to the solution and the wholeis stirred for several hours at 80-85.

The completely coppered amino disazo dyestuff is salted outwith amixture of sodium chloride and potassium chloride, filtered off anddissolved in 1000 parts of hot water. At 70, 21.8 parts of2,4,5,6-tetrachloropyrimidine are added and the pH is kept at 6.5 by thedropwise addition of 6 parts of sodium carbonate in parts of water. Assoon as there is no longer a free amino group, the dyestuif of theformula is salted out, dried in vacuo at 60 and milled. It is a blackishpowder which dissolves in water with a blackblue and in concentratedsulphuric acid with a greenish blue colour. It dyes natural orregenerated cellulose fibres from a soda alkaline dye liquor in reddishnavy blue shades which have excellent fastness to washing and EXAMPLE 1165.1 parts of the amino disazo dyestuff of the formula produced bycoupling the diazonium compound of 1-amino-4-acetylaminobenzene-Z-sulphonic acid with 1-amino-2-methoxy-S-methylbenzene in acetic acid medium, diazotising theamino azo dyestuif obtained, coupling with1-hydroxynaphthalene-3,6-disulphonic acid in the presence of sodiumcarbonate and saponifying the acylamino group with sodium hydroxide, aredissolved in 1000 parts of hot water. The solution is stirred forseveral hours at 85-90 with 200 parts of a solution containing 25 partsof crystallised copper sulphate and 100 parts of concentrated aqueousammonia, and with parts of dimethyl formamide.

On completion of the copper complex formation, the amino disazo dyestuffis precipitated by the addition of sodium chloride, filtered off andagain dissolved in 1000 parts of hot water. 21.8 parts of finelypulverised 2,4,5, 6- tetrachloropyrimidine are sprinkled into thissolution at and the pH of the dyestuif solution is kept at 6.5 by

the simultaneous addition dropwise of dilute sodium carbonate solution.

SOsH OCu O GE; H038 SOaH blue colour and dyes natural and regeneratedcellulose material from a soda alkaline dye liquor in navy blue shadeswhich have excellent fastness to washing and light.

Dyestufis having similarly good fastness properties are obtained if theamino disazo dyestuff described in this example is replaced by theequivalent amount of another amino disazo dyestufi formed from the diazoand coupling components given in columns II, III and IV of the followingTable II, and this is coppered and reacted with2,4,5,6-tetrachloropyrimidine.

solution, are dissolved in 1000 parts of hot water. 21.8 parts of finelypulverised 2,4,5,6-tetrachloropyrimidine are added to the solution at70, the pH of the dyestufi solution being kept at 6.5 by thesimultaneous addition dropwise of dilute sodium carbonate solution. Assoon as no more primary amine can be traced, parts of crystallisedcopper sulphate dissolved in 100 parts of Water, and also 40 parts ofcrystallised sodium acetate dissolved in 100 parts of Water are addedand the whole is stirred for 12 hours at 85-90".

TABLE II I II III IV V No. Diazonium compound from Component for theacetic acid Component for the alkaline coupling Shade on coupling cotton12 l-arlrliino4acgtylaminobenzene-Qsul- 1amino-2-methoxy-5-methy1benzenel-hydroxynaphthalene-3,6,8-trisulphonic acid Blue-grey.

p 01110 acl 13 do do 1,8-dg1ydroxynaphthalencfi-edisulphonic Grey-green.

aci 14 do .do 2-anigndti-hydroxynaphthalene-3,6-disu1phonic Do.

aci 15 d0 do 2-(3-solphophenylamino)8-hydroxynaphtha- Grey.

lcne-G-sulphonlc acid. 16 do l-amino-2,5-dimethoxybenzene ..do Greygreen, 17 do d0 Zaming-Et-hydroxynaphthalenc-3,6-disu1phon- Do.

1c aci 18 ..do .do 2-hydroxynaphthalene-3,fi-disulphonic aeid. Navyblue.

.,do .dlo 1hydroxynaphthalene-3,6,8-trisulph0nic acid Grey.amino-Eacetylaminohenzen do do Grey-blue.

phonic acid. 21 "do I-am1no-2-methoxy-methylbenzene do Navy blue.

1-hydroxynaphthalene-Bfidisulphonic acid. Do.

1,S-dinydroxynaphthalene-Ii,&disulphonic Navy blue.

2-amino-8-hydroxynaphthalene-3,6-disulacid.2-(3"sulphophenylamino)-8-hydroxynaphtha- Grey.

lene-fi-sulphonic acid.

Green-grey. phonic acid.

produced by coupling the diazo compound of l-a-mino-S-acetylaminohenzene 2-sulphonic acid with l-amino-Z- methoxynaphthalene 6sulphonic acid in acetic acid medium, diazotising the amino azo dyestuftobtained, coupling with 1,8-dihydroxynaphthalene-3,6-disulph0nic acid inthe presence of sodium carbonate and pyridine and saponifying theacetylamino group with sodium hydroxide On completion of the coppering,the dyestuif of the formula OH I is precipitated by the addition ofsodium chloride, isolated, dried in vacuo at 60 and milled. It is a darkpowder which dissolves in water with a blue-green colour. It dyesnatural or regenerated cellulose fibres from a soda alkaline dye liquidin greenish blue shades which have very good SOgH fastness to washingand light.

TABLE III I II III IV V N o. Diazonium compound from Component for theacetic acid Component for the alkaline coupling Shad c on couplingcotton 27 l-amino-5-acetylaminobcnzrme-2- 1amino2- uethoxynaphthalene-fil-hydroxynaphthalcne-3,8-disulphonic acidGreen-blue.

' sulphonic acid. sulphomc acid. 4

28 do do l-hydronynaphthalenc3,6-disu1pho111c ac1d- Do.

29 dn do a. l-hydroxynaphthalene-3,G,8-trisulphonic ac1d D0.

30 do de 2-acetylamino-6-hydroxynaphthalene-S-sul- Bluegrey.

phonic acid.

at dn do 2-(w-sulphoacetylamino)-6hydroxynaphtha- Green-grey.

lene-8-Sulphonic acid.

as d do 2-(w-sulphoacetylamino)8-hydroxytnaphtlia- Do.

lene-fi-sulphonic acid.

as (in do 2-(4-carboxyphenylamino)-8-hydroxynaph- Grey.

thalenc-S-sulphonic acid.

34.. do. do Q-amino-S-hydroxyuaphthalene-3,6-disul- Du.

phonic acid.

1-amino4-acetylaminobenzenc-2- do do Greengrey.

sulphonic acid.

do do Lsdgiydrosynaphthalene-3,(i-disulphonic acil-hydroxynaphthalene-E,8-disulphonic acid Dark green.l-hydroiq'naphthalene-3fi,8-ttisulph onic acid Olive green.I-hydroxynaphtl1alene3,6-clisulphonic acidh" Dark green.

I-hydroxynaphthalene-ti chlore-3,6-disul- Do. phonic acid. D

9 l Dyestuffs having similarly good fastness properties are and dyeingis continued for 1 hour at this temperature. obtained if, instead of theamino disazo dyestufi de- The dyeing is then rinsed and soaped' at theboil of 15 scribed in the above example, the equivalent amount ofminutes. .an amino disazo dyestuff produced with the components Dyeingshaving excellent fastness to washing and light mentioned in columns II,HI and IV of the preceding are obtained which are not noticeably changedeither in Table III is reacted under the conditions described in theshade or in fastness to light by finishing treatment with example with2,4,5,6-tetrochloropyrimidine and then consynthetic resin. verted intothe copper complex. We claim:

EXAMPLE 41 1. A fiber-reactive disazo-dyestuff which in its free acidform is of the formula The amino disazo dyestuff of the formula corn onson; 5 OH I I I I H N112 CH3 H033 SOsH wherein:

one of X and X represents hydrogen and the other the 2,4,5-trichloropyrimidyl- 6) -amino group,

is obtained by diazotising 3-nitro-1-aminobenzene and coupling it in amineral acid solution with 1-amino-2- methoxy-S-methylbenzene,diazotising the resulting amino Y represents a member selected ffom thegroup com monoazo dyestuif, coupling it in the presence of sodiumsisting of hydrogen lower alkyl lower alkoxy and bicarbonate, with 1hydroxynaphthalene-3,6,8:tnsulfon1c 3H acid and reducing the nitro groupthereof with sodium Z1 represents a member el ted from the groupconsulfide' sisting of hydrogen, lower alkyl, lower alkoxy,

65.1 parts of the amino disazo dyestulf thus prepared h drox 1Ower alkoxa d 1 6 1k are dissolved at 80 in 1000 parts of water, mixed withalykoxyyand y n Ow r a oxy ower 20 parts of ammonia and 25 parts ofcopper sulfate and Z re presents hydrogen, and stirred for 8 hours at 80to 85. The cupriferous dyestuff and Z taken to ether re re em th on,begins to separate. It is completely precipitated by the 1 2 g p S 6 grping addition of sodium chloride, separated by filtration and--CH=CCH=CH dissolved in 600 parts of water at 90. Then, 21.8 parts of2,4,5,6 tetrachloropyrimidine are added, and the pH- 1 S0311 value ismaintained at 6.5 by gradual dropwise addition R i a member selectedfrom the group consisting of of 6 parts of sodium carbonate in 40 partsof water. hydrogen, lower alkyl, hydroxy-lower alkoxy and After 10hours, the dyestutf of the formula lower alkoxy-lower alkoxy, and c1 01xi f N NH OCu0 S0311 40 ts lthd hthl d'l C1 N:N N:N represen a monova eny roxynap y ra ica the hydroxyl group of which is in ortho-position to ithe azo bridge linked to A,

the total number of SO H groups ranging from 2 to 4 at least 2 of whichare linked to A.

2. A fiber-reactive disazo-dyestuff which in its free acid form is ofthe formula 3 OaS SOaH is precipitated with sodium chloride, separationby filtration, dried in vacuo at 80 and ground. It yields a dark powderdissolving in water with a blue shade, in concentrated sulfuric acidwith a greenish-blue shade. From a Glauber-salt-containing dye hath madealkaline with Y O (.M O sodium hydroxide, it dyes cellulose fibres indeep pure- 5 I reddish navy blue shades which have excellent fastnessN=N to light and washing.

Dyestuffs with similar good properties are obtained if, (m) instead ofthe amino disazo dyestuff described in the example, equivalent amountsof another amino disazo dyewherein: stuff prepared of the componentslisted in Table IV are one of X and X represents hydrogen and the othertreated in the same way with copper sulfate and reacted the2,4,S-trichloropyrimidyl-(6)-amino group, with2,4,5,6-tetrachloropyrimidine. Y "represents a member selected from thegroup con- TABLE IV No. N itrodiazonium compound from- Component for thecongo-acid Component for the alkaline coupling Shade on coupling cotton42 l-amino-3nitrobenzene 1-amin0-2,fi-dimethoxybenzene1-hydroxynaphthalene-3,6,8-trisulphonic acid Grgtlen' h navy I19. 43"...l-amino--nitrobenzene do do Olive green. 44 dl-arnino-Z-methoxy-5-methylbenzene do Reddish navy blue. 45"...l-amino-Ii-nitrobenzene 1-amin0-2-ethoxybenzene do D0. 46"...1-amino-2-methyl5-nitrobenzene 1amino-2-methoxy-5-methylbenzene do Navyblue.

EXAMPLE 47 sisting of hydrogen, lower alkyl, lower alkoxy and A dyebathis prepared by dissolving 2 parts of the 803E, dystulf described inexample 1 in 1000 parts of water 1 fefiresents a member Selected fromthe group and adding 20 parts of sodium carbonate. 100 parts of slstlngof hydrogen, lower alkyl, lower alkoxy, cotton are introduced at 40, thebath is heated to 9095 y 0XY-10WeF alkoxy and lower xy-l w r within 30minutes, 80 parts of sodium sulphate are added alkoxy, and

1 1 1 2 Z represents hydrogen, and 3. A disazo dyestufr which in itsfree acid form is of Z and Z taken together represent the grouping theformula -CH=CJCH=CH- o--Cu0 S0311 $0311 I I i and 0 5 Cl 01 N=N N=N J 1i1 IH (3H3 H038 -som represents a divalent oxynaphthyl radical whereof Nthe oxygen is linked to A in ortho-position to the u azo bridge linkedto A, 10 the total number of --SO H groups ranging from 2 to 4. A disazodyestuff which in its free acid form is of 4 at least 2 of which arelinked to A. the formula C1 C1 0H3 OCu (1) 51.0335

G N -NH N=N N=N N C1 H035 $0311 5. A disazo dyestuff which in its freeacid form is of the formula 6. A disazo dyestuff which in its free acidform is of 7. A disazo dyestufif which in its free acid form is of theformula References Cited UNITED STATES PATENTS 3,234,204 2/1966 Benz eta1 260146 FOREIGN PATENTS 242,902 12/ 1962 Australia.

CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner.

